CN111995747B - Preparation method and application of reactive flame retardant for polyamide - Google Patents
Preparation method and application of reactive flame retardant for polyamide Download PDFInfo
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- CN111995747B CN111995747B CN202010968701.XA CN202010968701A CN111995747B CN 111995747 B CN111995747 B CN 111995747B CN 202010968701 A CN202010968701 A CN 202010968701A CN 111995747 B CN111995747 B CN 111995747B
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- flame retardant
- polyamide
- chloroacetate
- dopo
- reactive flame
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/42—Polyamides containing atoms other than carbon, hydrogen, oxygen, and nitrogen
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
- C07F9/657172—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and one oxygen atom being part of a (thio)phosphinic acid ester: (X = O, S)
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/07—Addition of substances to the spinning solution or to the melt for making fire- or flame-proof filaments
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
- D01F6/80—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyamides
Abstract
The invention relates to a preparation method and application of a reactive flame retardant for polyamide. The method comprises the following steps: putting a certain amount of DOPO-HQ and an acid-binding agent in a corresponding proportion into a three-neck flask, adding a solvent for dissolving, dropwise adding a certain amount of chloroacetate under the condition of 50-140 ℃, reacting for 4-24 hours, then carrying out rotary evaporation to remove the solvent and unreacted chloroacetate, adding an ethanol solution of sodium hydroxide with the molar mass 2.5 times that of the DOPO-HQ to hydrolyze ester bonds of an obtained intermediate, adding hydrochloric acid to adjust the pH =1, filtering, washing for 3 times with secondary water, and drying to obtain the reactive flame retardant for the polyamide. The yield of the product is 52-68%.
Description
Technical Field
The invention belongs to the technical field of preparation of a reactive flame retardant for polyamide, and particularly relates to a reactive flame retardant for polyamide, a preparation method of the reactive flame retardant and application of the reactive flame retardant in polyamide.
Background
The polyamide fiber has the advantages of high breaking strength, good wear resistance, low density, high moisture absorption, good dyeing and the like, and has irreplaceable status in the fields of high-end clothing, military police articles, industrial yarn and the like. However, the polyamide fiber, which is a main kind of chemical fiber, has difficulty in achieving a desired flame retardant effect because: usually, a high content of flame retardant is added to achieve the flame retardant performance meeting the requirement, and the amido bond is active and is easy to generate chemical reaction with the flame retardant and cause molecular chain degradation at the spinning temperature of about 260-320 ℃. Therefore, the spinnability of the polyamide and the physical and mechanical properties of the polyamide fiber are easily deteriorated due to flame retardant modification, so that the preparation technology requirement of the flame retardant polyamide fiber is high, the control difficulty is high, most of the research and development of the flame retardant polyamide at home and abroad are concentrated in the resin field, and no example of successful development of commercial products of the flame retardant polyamide fiber is found.
The 10- (2, 5-dihydroxyphenyl) -10-hydrogen-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO-HQ) is a phosphaphenanthrene reaction type flame retardant, is commonly used as a flame retardant and a curing agent of high-end epoxy resin such as copper clad laminates, semiconductor packaging and the like, and has the advantages of low addition amount, good flame retardant effect, no influence on the mechanical properties of materials and the like. Moreover, DOPO-HQ also exhibits its excellent flame retardant properties in other polymers such as polyurethane, polylactic acid, and the like. However, the introduction of DOPO-HQ into polyamides presents significant problems: when the flame retardant is added as an additive flame retardant, the mechanical property of polyamide is obviously deteriorated; the phenolic hydroxyl group has low activity and can not be taken as a copolymerization structure to be introduced into the main chain of the polyamide.
Disclosure of Invention
The invention aims to solve the problems in the prior art, and firstly provides a reactive flame retardant for polyamide.
The invention also aims to provide a preparation method of the reactive flame retardant.
The invention provides a reactive flame retardant for polyamide, which is characterized in that the structure of the flame retardant for polyamide is as follows:
the preparation method of the reactive flame retardant for polyamide is characterized by comprising the following process steps and conditions:
putting a certain amount of DOPO-HQ and an acid-binding agent in a corresponding proportion into a three-neck flask, adding a solvent for dissolving, dropwise adding a certain amount of chloroacetate at 50-140 ℃, reacting for 4-24 hours, then removing the solvent and unreacted chloroacetate by rotary evaporation, adding an ethanol solution of sodium hydroxide with 2.5 times of molar mass of the DOPO-HQ to hydrolyze ester bonds of an obtained intermediate, adding hydrochloric acid to adjust the pH =1, filtering, washing for 3 times with secondary water, and drying to obtain the reactive flame retardant for polyamide.
The acid-binding agent used in the method is one or more of triethylamine, sodium carbonate, potassium carbonate or pyridine.
The solvent used in the method is one or more of ethanol, ethylene glycol ethyl ether, 1, 4-dioxane, toluene, acetonitrile or acetone.
The chloroacetate used in the above method is any one of methyl chloroacetate, ethyl chloroacetate, or propyl chloroacetate.
The molar ratio of DOPO-HQ to chloroacetate used in the above process is 1:2 to 5.
Compared with the prior art, the invention has the following beneficial effects:
1. the flame retardant provided by the invention solves the problem that DOPO-HQ cannot be used for flame retardance of polyamide.
2. The polyamide fiber added with the flame retardant has the advantages of good flame retardant property, excellent mechanical property, strong spinnability and the like.
3. The flame retardant provided by the invention is a reactive flame retardant, does not contain halogen, and meets the requirement of environmental protection.
4. The preparation method provided by the invention is simple, easy to control and convenient to popularize and use.
Drawings
FIG. 1 is a NMR chart of a reactive flame retardant for polyamide prepared in example 2 of the present invention.
Detailed Description
The invention is further illustrated by the following examples. It should be noted that the examples given are not to be construed as limiting the scope of the invention, and that those skilled in the art, on the basis of the teachings of the present invention, will be able to make numerous insubstantial modifications and adaptations of the invention without departing from its scope.
Example 1
Adding 0.4mol of DOPO-HQ, 0.8mol of triethylamine and sufficient toluene into a three-neck flask, heating to 110 ℃, dropwise adding 1mol of propyl chloroacetate after the DOPO-HQ is completely dissolved, keeping the temperature for reacting for 8 hours after dropwise adding for 1 hour, and removing the solvent and the redundant propyl chloroacetate by rotary evaporation. And adding an ethanol solution containing 1mol of sodium hydroxide, stirring for hydrolysis for 2 hours, then dripping hydrochloric acid to adjust the pH value to be =1, filtering, washing with secondary water for three times, and drying to obtain the flame retardant, wherein the yield is 84%.
Example 2
Adding 0.4mol of DOPO-HQ, 0.4mol of potassium carbonate and sufficient acetonitrile into a three-neck flask, heating to 90 ℃, dropwise adding 2mol of methyl chloroacetate after the DOPO-HQ is completely dissolved, reacting for 14 hours after dropwise adding for 2 hours, and removing the solvent and the redundant methyl chloroacetate by rotary evaporation. Adding an ethanol solution containing 1mol of sodium hydroxide, stirring for hydrolysis for 2 hours, then dripping hydrochloric acid to adjust the pH to be =1, filtering, washing with secondary water for three times, and drying to obtain the flame retardant with the yield of 89%.
FIG. 1 is a NMR chart of a reactive flame retardant for polyamide prepared in example 2 of the present invention. In the figure, the peak of 4.0-5.0 ppm is attributed to H of methylene in chloroacetate, C-H on aromatic ring in DOPO-HQ at 6.5-8.5 ppm, and absorption peak of COOH at about 13ppm, and the above results prove the successful preparation of the flame retardant.
Example 3
Adding 0.4mol of DOPO-HQ, 0.4mol of sodium carbonate and sufficient ethylene glycol ethyl ether into a three-neck flask, heating to 140 ℃, dropwise adding 1.5mol of ethyl chloroacetate after the DOPO-HQ is completely dissolved, keeping the temperature for reacting for 4 hours after dropwise adding for 1.5 hours, and removing the solvent and the redundant ethyl chloroacetate by rotary evaporation. And adding an ethanol solution containing 1mol of sodium hydroxide, stirring for hydrolysis for 2 hours, then dripping hydrochloric acid to adjust the pH value to be =1, filtering, washing with secondary water for three times, and drying to obtain the flame retardant with the yield of 72%.
Example 4
Adding 0.4mol of DOPO-HQ, 0.8mol of pyridine and sufficient acetone into a three-neck flask, heating to 50 ℃, dropwise adding 1.2mol of ethyl chloroacetate after the DOPO-HQ is completely dissolved, keeping the temperature for reacting for 23 hours after dropwise adding is finished for 1 hour, and removing the solvent and the redundant ethyl chloroacetate by rotary evaporation. Adding an ethanol solution containing 1mol of sodium hydroxide, stirring for hydrolysis for 2 hours, then dripping hydrochloric acid to adjust the pH =1, filtering, washing with secondary water for three times, and drying to obtain the flame retardant with the yield of 88%.
Example 5
Adding 0.4mol of DOPO-HQ, 0.8mol of triethylamine and sufficient ethanol into a three-neck flask, heating to 80 ℃, dropwise adding 1.8mol of methyl chloroacetate after the DOPO-HQ is completely dissolved, keeping the temperature for reacting for 16 hours after dropwise adding is finished for 2 hours, and removing the solvent and the redundant methyl chloroacetate by rotary evaporation. And adding an ethanol solution containing 1mol of sodium hydroxide, stirring for hydrolysis for 2 hours, then dripping hydrochloric acid to adjust the pH to be =1, filtering, washing with secondary water for three times, and drying to obtain the flame retardant with the yield of 74%.
Application example 1
Mixing the flame retardant of the embodiment 2 and hexamethylenediamine according to a molar ratio of 1.5, adding deionized water accounting for 30wt% of the total mass of the system as a reaction solvent, and heating and stirring under the protection of nitrogen at a stirring speed of 50r/min; keeping the pressure at 1.5MPa after the temperature is raised to 200 ℃, and keeping the temperature and the pressure for 1h; reducing the pressure to normal pressure within 0.5h, reducing the stirring speed to 30r/min, vacuumizing to-0.05 MPa, and keeping for 0.5h; stopping stirring, standing for 10-15 min, and discharging under the protection of nitrogen to obtain the flame retardant salt.
Mixing 97 parts by weight of adipic acid hexamethylene diamine salt and 3 parts by weight of flame retardant salt, adding a proper amount of adipic acid to ensure that the molar ratio of terminal amino groups to terminal carboxyl groups in a system is 1.01, adding deionized water accounting for 60% of the total mass of the system, and heating and stirring under the protection of nitrogen at the stirring speed of 200r/min; keeping the pressure at 1.85MPa after the temperature is raised to 210 ℃, and keeping the temperature and the pressure for 1h; reducing the stirring speed to 100r/min, and reducing the pressure to normal pressure within 2 hours; reducing the stirring speed to 50r/min, vacuumizing to 0.08MPa and keeping for 1h; stopping stirring, standing for 10-15 min, and discharging under the protection of nitrogen to obtain the flame-retardant polyamide 66 with the limiting oxygen index of 28%.
Application example 2
Mixing the flame retardant of the embodiment 2 and glutaric acid in an equal molar ratio, adding deionized water accounting for 30wt% of the total mass of the system as a reaction solvent, and heating and stirring at the stirring speed of 50r/min under the protection of nitrogen; keeping the pressure at 1.5MPa after the temperature is raised to 200 ℃, and keeping the temperature and the pressure for 1h; reducing the pressure to normal pressure within 0.5h, reducing the stirring speed to 30r/min, vacuumizing to-0.07 MPa, and keeping for 1h; stopping stirring, standing for 10-15 min, and discharging under the protection of nitrogen to obtain the flame retardant salt.
Mixing 95 parts of caprolactam and 5 parts of flame retardant salt according to parts by weight, adding a proper amount of hexamethylenediamine to ensure that the molar ratio of terminal amino groups to terminal carboxyl groups in a system is 1.1, then adding deionized water accounting for 5% of the total mass of the system, and heating and stirring under the protection of nitrogen, wherein the stirring speed is 100r/min; keeping the pressure at 0.6MPa after the temperature is increased to 200 ℃, and keeping the temperature and the pressure for 1h; reducing the pressure to normal pressure within 0.5h; reducing the stirring speed to 50r/min, and introducing nitrogen to react for 3 hours; vacuumizing to-0.05 MPa and keeping for 1.5h; stopping stirring, standing for 10-15 min, and discharging under the protection of nitrogen to obtain the flame-retardant polyamide 6 with the limiting oxygen index of 29%.
Claims (7)
1. A reactive flame retardant for polyamide is characterized in that the structure of the flame retardant for polyamide is as follows:
2. the method for preparing a reactive flame retardant for polyamide as claimed in claim 1, wherein the method comprises the following steps and conditions:
adding DOPO-HQ and an acid-binding agent into a container, adding a solvent for dissolving, dropwise adding chloroacetic ester under the condition of 50-140 ℃, reacting for 4-24 hours, performing rotary evaporation to remove the solvent and unreacted chloroacetic ester, adding an ethanol solution of sodium hydroxide with the molar weight 2.5 times that of the DOPO-HQ, hydrolyzing ester bonds of the obtained intermediate, adding hydrochloric acid for adjusting the pH =1, filtering, washing for 3 times with water for the second time, and drying to obtain the reactive flame retardant for the polyamide.
3. The method for preparing the reactive flame retardant for polyamide as claimed in claim 2, wherein the acid-binding agent is one or more of triethylamine, sodium carbonate, potassium carbonate or pyridine.
4. The method of claim 2, wherein the solvent is one or more of ethanol, ethylene glycol ethyl ether, 1, 4-dioxane, toluene, acetonitrile, or acetone.
5. The method of claim 2, wherein the chloroacetate is any one of methyl chloroacetate, ethyl chloroacetate, and propyl chloroacetate.
6. The method for producing a reactive flame retardant for polyamide as claimed in claim 2, wherein the molar ratio of DOPO-HQ to chloroacetate is 1:2 to 5.
7. Use of the flame retardant of claim 1 for the preparation of polyamides.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010968701.XA CN111995747B (en) | 2020-09-15 | 2020-09-15 | Preparation method and application of reactive flame retardant for polyamide |
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| CN202010968701.XA CN111995747B (en) | 2020-09-15 | 2020-09-15 | Preparation method and application of reactive flame retardant for polyamide |
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| CN111995747B true CN111995747B (en) | 2022-12-02 |
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| CN112679538B (en) * | 2020-12-29 | 2022-10-04 | 湖北省兴发磷化工研究院有限公司 | Synthesis method and application of dibasic acid ester oligomer flame retardant |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1075848A (en) * | 1975-10-14 | 1980-04-15 | Takao Kashihara | New-phosphorus-containing compounds |
| JPS61118393A (en) * | 1984-11-15 | 1986-06-05 | Nippon Ester Co Ltd | Lower aliphatic dicarboxylic acid ester of phosphinic acid and preparation thereof |
| WO2004111121A1 (en) * | 2003-06-12 | 2004-12-23 | Fuji Electric Holdings Co., Ltd. | Reactive flame retardants and flame-retarded resin products |
| CN102875982A (en) * | 2012-10-15 | 2013-01-16 | 宁波优科泰科技发展有限公司 | In-situ modified halogen-free flame retardant thermoplastic resin composition and preparation method thereof |
| CN106832911A (en) * | 2017-01-06 | 2017-06-13 | 东华大学 | A kind of Flameproof polyamide 66 and preparation method thereof |
-
2020
- 2020-09-15 CN CN202010968701.XA patent/CN111995747B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1075848A (en) * | 1975-10-14 | 1980-04-15 | Takao Kashihara | New-phosphorus-containing compounds |
| JPS61118393A (en) * | 1984-11-15 | 1986-06-05 | Nippon Ester Co Ltd | Lower aliphatic dicarboxylic acid ester of phosphinic acid and preparation thereof |
| WO2004111121A1 (en) * | 2003-06-12 | 2004-12-23 | Fuji Electric Holdings Co., Ltd. | Reactive flame retardants and flame-retarded resin products |
| CN102875982A (en) * | 2012-10-15 | 2013-01-16 | 宁波优科泰科技发展有限公司 | In-situ modified halogen-free flame retardant thermoplastic resin composition and preparation method thereof |
| CN106832911A (en) * | 2017-01-06 | 2017-06-13 | 东华大学 | A kind of Flameproof polyamide 66 and preparation method thereof |
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